Conventionally, metallic vanadium is produced from vanadium pentoxide (V2O5). Sodium metavanadate (NaVO3) is an essential intermediate product for the V2O5 production. A novel environmentally friendly route for the metallic vanadium preparation from NaVO3 by molten salt electrolysis is proposed. In the NaCl molten salt, NaVO3 has a high solubility of 8.6 mol% (163 wt.%) at 1173 K and was easily electro-reduced to V2O3. However, V2O3 is almost insoluble in the NaCl molten salt, and thus can't be further electro-reduced to metallic vanadium. In the eutectic CaCl2-NaCl molten salt, NaVO3 was converted to CaV2O6. CaV2O4 as the intermediate product was produced during CaV2O6 electrolysis and can be dissolved into the eutectic CaCl2-NaCl molten salt. The dissolved CaV2O4 was further electro-reduced to metallic vanadium. (C) 2015 Elsevier Ltd. All rights reserved.